Ambient-Visible-Light-Mediated Enhanced Degradation of UV Stabilizer Bis(4-hydroxyphenyl)methanone by Nanosheet-Assembled Cobalt Titanium Oxide: A Comparative and DFT-Assisted Investigation

Bis(4-hydroxyphenyl)methanone (BHPM), a common ultraviolet stabilizer and filter (USF), is extensively added in sunscreens; however, BHPM is proven as an endocrine disruptor, posing a serious threat to aquatic ecology, and BHPM should be then removed. As sulfate radical (SO4 center dot-) could be useful for eliminating emerging contaminants, oxone appears as a favorable source reagent of SO4 center dot- for degrading BHPM. Even though cobalt is a useful catalyst for activating oxone to generate SO4 center dot-, it would be even more promising to utilize ambient-visible-light irradiation to enhance oxone activation using cobaltic catalysts. Therefore, in contrast to the conventional cobalt oxide, cobalt titanium oxide (CTO) was investigated for chemical and photocatalytic activation of oxone to eliminate BHPM from water. Especially, a special morphology of nanosheet-assembled configuration of CTO was designed to maximize active surfaces and sites of CTO. Thus, CTO outperforms Co3O4 and TiO2 in degrading BHPM via oxone activation. Furthermore, the substituent of Ti enabled CTO to enhance absorption of visible light and possessed a much smaller E-g. These photocatalytic properties intensified CTO's activity for oxone activation. CTO possessed a significantly smaller E-a of degradation of USFs than other catalytic systems. Mechanistic insight for degrading BHPM by CTO + oxone was explicated for identifying contribution of reactive oxygen species to BHPM degradation. The BHPM degradation pathway was also investigated and unveiled in details via the DFT calculation. These results validated that CTO is a superior cobaltic alternative for activating oxone to eliminate BHPM.